Patent Application
20240174812
The present invention relates to a leveling agent that can be used to lower the flat ratio of a circuit pattern (i.e. the height deviation ratio of a circuit pattern) formed by a patterning process such as a semi-additive process (SAP) or a modified semi-additive process (MSAP) and minimize the difference in the plating thickness of the circuit pattern, and an electroplating composition including the leveling agent.
With the trend toward miniaturization and integration of electronic products, printed circuit boards have also been miniaturized and integrated. Various processes for forming circuit patterns on printed circuit boards are known, for example, subtractive, semi-additive (SAP), and modified semi-additive processes (MSAP).
According to the subtractive process, electrolytic copper is used for panel plating on an existing copper foil in a copper clad laminate (CCL), resulting in an increase in the total thickness of the copper foil. Etching of the thick copper foil to form a fine circuit pattern is limited due to etching factors.
Thus, a SAP or MSAP process is currently used to form fine a circuit pattern. According to the SAP or MSAP process, a seed layer is formed by electroless plating, a photoresist (PR) circuit pattern is formed thereon, followed by electroplating to form a circuit pattern.
The circuit pattern formed by the above process may have various line widths W1, W2, and W3, as shown in
(Patent Document 1) Korean Patent Publication No. 2012-0095888
The present invention intends to provide a leveling agent that can control the height deviation of a circuit pattern during plating for forming the circuit pattern.
The present invention also intends to provide an electroplating composition including the leveling agent.
One aspect of the present invention provides a leveling agent represented by Formula 1:
wherein X1 and Y1 are each independently selected from the group consisting of C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, A1 is a single bond or is selected from the group consisting of oxygen (O), sulfur (S), carbonyl (C═O), NR1, C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, R1 is selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, and n and m are each independently an integer from 0 to 10, with the proviso that at least one of n and m is 1 or more,
or including at least one structural unit selected from the group consisting of those represented by Formulae 2 to 5:
wherein A2 to A5 are each independently a single bond or is selected from the group consisting of oxygen (O), sulfur (S), NR2, carbonyl (C═O), C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, R2 is selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, L1 and L2 are each independently selected from the group consisting of C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, each R3 is independently selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, n and m are each independently an integer from 0 to 10, with the proviso that at least one of n and m is 1 or more, and each z is independently an integer from 1 to 10, with the proviso that the alkyl, aryl or heteroaryl group as each of X1 and Y1, the alkylene, arylene or heteroarylene group as A1, the alkylene, arylene or heteroarylene group as each of A2 to A5, the alkylene, arylene or heteroarylene group as each of L1 and L2, and the alkyl, aryl or heteroaryl group as each of R1 to R3 are each independently optionally substituted with one or more substituents selected from the group consisting of halogen groups, C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups.
A1 in Formula 1 may be selected from the group consisting of imidazole, benzimidazole, and pyridine groups.
A2 in Formula 2 may be represented by S-1 or S-2:
wherein A2′ is selected from the group consisting of C6-C20 arylene groups and C2-C20 heteroarylene groups and L3 and L4 are each independently a C1-C10 alkylene group.
A3 in Formula 3 may be NR2 wherein R2 may be a C2-C20 heteroaryl group.
A4 in Formula 4 may be NR2 wherein R2 may be a C2-C20 heteroaryl group and L1 and L2 in Formula 4 may each independently be a C1-C10 alkylene group.
A5 in Formula 5 may be carbonyl (C═O) and L1 and L2 in Formula 5 may each independently be a C1-C10 alkylene group.
Another aspect of the present invention provides an electroplating composition including a metal ion source and the leveling agent.
The alkyl groups are intended to include linear and branched ones. Specific examples of the alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and pentyl groups.
The aryl groups may be, for example, phenyl, naphthyl, biphenyl, anthracene, and phenanthrene groups but are not limited thereto.
The heteroaryl groups may be monovalent aromatic cyclic groups interrupted by at least one heteroatom such as N, O, S or F.
The alkylene groups are intended to include linear and branched ones. Specific examples of the alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, and pentylene groups.
The arylene groups may be, for example, phenylene, naphthylene, and biphenylene groups but are not limited thereto.
The heteroarylene groups may be divalent aromatic cyclic groups interrupted by at least one heteroatom such as N, O, S or F.
The halogen groups may be, for example, fluoro, bromo, chloro, and iodo groups.
The leveling agent of the present invention can uniformly control the degree of adsorption of metal ions on a target substrate due to the presence of an alkyl structure and nitrogen atoms in the molecular structure. Therefore, metal ions can be uniformly adsorbed in a circuit pattern formed with the electroplating composition including the leveling agent according to the present invention even when different current densities are applied depending on the line widths of the circuit pattern, so that the circuit pattern has a minimal height deviation (a constant height). In conclusion, the use of the electroplating composition can provide a printed circuit board with improved performance and reliability.
These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
It should be understood that the terms and words used in the specification and the claims are not to be construed as having common and dictionary meanings but are construed as having meanings and concepts corresponding to the technical spirit of the present invention in view of the principle that the inventor can define properly the concept of the terms and words in order to describe his/her invention with the best method.
The present invention is directed to a leveling agent that can control the degree of adsorption of metal ions during plating for forming a circuit pattern, allowing the circuit pattern to have a uniform (constant) height and square shape even though the circuit pattern has various line widths, and an electroplating composition including the leveling agent.
The present invention will now be described in detail.
Specifically, the present invention provides a leveling agent represented by Formula 1:
wherein X1 and Y1 are each independently selected from the group consisting of C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, A1 is a single bond or is selected from the group consisting of oxygen (O), sulfur (S), carbonyl (C═O), NR1, C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, R1 is selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, and n and m are each independently an integer from 0 to 10, with the proviso that at least one of n and m is 1 or more,
or including at least one structural unit selected from the group consisting of those represented by Formulae 2 to 5:
wherein A2 to A5 are each independently a single bond or is selected from the group consisting of oxygen (O), sulfur (S), NR2, carbonyl (C═O), C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, R2 is selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, L1 and L2 are each independently selected from the group consisting of C1-C10 alkylene groups, C6-C20 arylene groups, and C2-C20 heteroarylene groups, each R3 is independently selected from the group consisting of hydrogen (H), C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups, n and m are each independently an integer from 0 to 10, with the proviso that at least one of n and m is 1 or more, and each z is independently an integer from 1 to 10, with the proviso that the alkyl, aryl or heteroaryl group as each of X1 and Y1, the alkylene, arylene or heteroarylene group as A1, the alkylene, arylene or heteroarylene group as each of A2 to A5, the alkylene, arylene or heteroarylene group as each of L1 and L2, and the alkyl, aryl or heteroaryl group as each of R1 to R3 are each independently optionally substituted with one or more substituents selected from the group consisting of halogen groups, C1-C10 alkyl groups, C6-C20 aryl groups, and C2-C20 heteroaryl groups.
Specifically, A1 in Formula 1 may be selected from the group consisting of imidazole, benzimidazole, and pyridine groups.
A2 in Formula 2 may be represented by S-1 or S-2:
wherein A2′ is selected from the group consisting of C6-C20 arylene groups and C2-C20 heteroarylene groups and L3 and L4 are each independently a C1-C10 alkylene group. Specifically, A2′ may be a phenylene group and L3 and L4 may each independently be an ethylene or propylene group.
In the structure represented by S-1 or S-2, asterisks (*) represent bonding positions but are omitted here.
A3 in Formula 3 may be NR2 wherein R2 may be a C2-C20 heteroaryl group. Specifically, R2 may be a pyridine group.
A4 in Formula 4 may be NR2 wherein R2 may be a C2-C20 heteroaryl group. Specifically, R2 may be a pyridine group. L1 and L2 in Formula 4 may each independently be a C1-C10 alkylene group. Specifically, L1 and L2 may each independently be an ethylene or propylene group.
A5 in Formula 5 may be carbonyl (C═O) and L1 and L2 in Formula 5 may each independently be a C1-C10 alkylene group. Specifically, L1 and L2 may each independently be an ethylene, propylene, butylene or pentylene group.
Hydrogen atoms (H) may be bonded to both ends of each of the structural units represented by Formulae 2 to 5.
In a specific embodiment, the leveling agent of the present invention may be a compound including at least one structural unit selected from those represented by C-1 to C-6:
wherein each z is independently an integer from 1 to 10, but is not limited thereto.
There is no particular restriction on the method for synthesizing the leveling agent of the present invention. The leveling agent of the present invention can be synthesized with high efficiency by reacting an alkylation agent with an amine compound in the presence of a solvent. Specifically, the leveling agent of the present invention can be synthesized by dissolving an alkylation agent in a solvent, adding an amine compound to the solution, and allowing the reaction to proceed. Here, the alkylation agent can be defined as a compound that adds an alkyl or alkylene group to the molecule of the amine compound through a substitution reaction with the amine compound.
The alkylation agent is not particularly limited and may be selected from the group consisting of 1,2-bis(2-chloroethoxy)ethane, dichloro-m-xylene, 1,3-dichloro-2-propanol, 1,4-butanediol, poly(propylene glycol)diglycidyl ether, 1,6-hexanediol, and mixtures thereof.
The amine compound is not particularly limited and may be selected from the group consisting of benzimidazole, aminopyridine, 2,6-diaminopyridine, urea, thiourea, aniline, 1,3-diphenylurea, and mixtures thereof.
There is no particular restriction on the dissolution temperature of the alkylation agent in the solvent. The dissolution temperature may be 45 to 110° C., specifically 50 to 100° C.
The alkylation agent may react with the amine compound in a weight ratio of 4:1 to 3:2. However, there is no particular restriction on the ratio between the alkylation agent and the amine compound that react with each other.
The alkylation agent may react with the amine compound for 9 to 12 hours but the reaction time is not particularly limited.
The solvent used to dissolve the alkylation agent is not particularly limited and may be any of those commonly known in the art. The solvent may be selected from the group consisting of aqueous solvents (e.g., water, purified water, and deionized water), alcoholic solvents (e.g., ethanol and methanol), glycol-based solvents (e.g., ethylene glycol and propylene glycol), and mixtures thereof, for example, taking into consideration the solubility of the alkylation agent and the synthesis efficiency of the leveling agent.
The leveling agent of the present invention may be a monomer obtained by the above synthetic method or a polymer obtained by polymerization of the monomer.
The present invention also provides an electroplating composition including the leveling agent. Specifically, the electroplating composition of the present invention includes the leveling agent and a metal ion source.
The leveling agent included in the electroplating composition of the present invention has been described above and thus will be omitted. The concentration (content) of the leveling agent is not particularly limited and may be 5 to 20 ml/L, specifically 8 to 12 ml/L, for example, taking into consideration the uniformity of a circuit pattern and the plating efficiency.
The metal ion source included in the electroplating composition of the present invention serves as a source for metal ions in the composition and may be any of those commonly known in the art. Specifically, the metal ion source may be a copper ion source. The concentration (content) of the metal ion source is not particularly limited and may be 50 to 250 g/L, specifically 100 to 150 g/L, for example, taking into consideration the uniformity and density of a circuit pattern.
The electroplating composition of the present invention may further include at least one component selected from the group consisting of strong acids, halogen ion sources, brighteners, and carriers, which can be used to increase the physical properties of the electroplating composition.
The electroplating composition of the present invention may further include a strong acid that serves as an electrolyte as well as a pH-adjusting agent. The strong acid may be any of those commonly known in the art. Specifically, the strong acid may be selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, sulfonic acid, hydrobromic acid, fluoroboric acid, and mixtures thereof. The concentration (content) of the strong acid is not particularly limited and may be 50 to 250 g/L, specifically 100 to 150 g/L, for example, taking into consideration the pH of the electroplating composition.
The electroplating composition of the present invention may further include a halogen ion source that serves as a source for halogen ions in the composition. The halogen ion source may be any of those commonly known in the art, specifically a chlorine ion source. The concentration (content) of the halogen ion source is not particularly limited and may be 30 to 60 mg/L, specifically 40 to 50 mg/L, for example, taking into consideration the uniformity and density of a circuit pattern.
The electroplating composition of the present invention may further include a brightener that increases the reduction rate of metal ions for fast plating. The brightener may be any of those commonly known in the art. Specifically, the brightener may be selected from the group consisting of bis(3-sulfopropyl)disulfide (sodium salt), 3-mercapto-1-propanesulfonic acid (sodium salt), 3-amino-1-propanesulfonic acid, O-ethyl-S-(3-sulphopropyl)dithiocarbonate (sodium salt), 3-(2-benzothiazolyl-1-thio)-1-propanesulfonic acid (sodium salt), N,N-dimethyldithiocarbamic acid-(3-sulfopropyl)ester (sodium salt), and mixtures thereof. The concentration (content) of the brightener is not particularly limited and may be 0.5 to 5 ml/L, specifically 1 to 3.5 ml/L, for example, taking into consideration the plating speed of the composition.
The electroplating composition of the present invention may further include a carrier that serves to increase the surface flatness of a circuit pattern. The carrier may be any of those commonly known in the art. The concentration (content) of the carrier is not particularly limited and may be 5 to 15 ml/L, specifically 8 to 12 ml/L, for example, taking into consideration the uniformity of a circuit pattern and the plating efficiency.
The electroplating composition of the present invention can be used in various processes for forming circuit patterns. Specifically, the electroplating composition of the present invention can be used in a SAP or MSAP process for forming a circuit pattern. However, the electroplating composition of the present invention can also be utilized in plating processes for forming plating films having uniform thicknesses as well as plating processes for forming circuit patterns.
1,2-Bis(2-chloroethoxy)ethane (A) was added to and completely dissolved in ethylene glycol at a temperature of about 90-100° C. Next, benzimidazole (B) was added in a weight ratio of 4:1 (A:B) relative to the 1,2-bis(2-chloroethoxy)ethane. The reaction was allowed to proceed for about 9-12 h to synthesize a leveling agent.
A leveling agent was synthesized in the same manner as in Example 1, except that dichloro-m-xylene and aminopyridine were used instead of 1,2-bis(2-chloroethoxy)ethane and benzimidazole, respectively.
A leveling agent was synthesized in the same manner as in Example 1, except that 1,3-dichloro-2-propanol and 2,6-diaminopyridine were used instead of 1,2-bis(2-chloroethoxy)ethane and benzimidazole, respectively.
1,3-Dichloro-2-propanol (A) was added to water and refluxed at about 100° C. for complete dissolution. Next, 2,6-diaminopyridine (B) was added in a weight ratio of 4:1 (A:B) relative to the 1,3-dichloro-2-propanol. The reaction was allowed to proceed for about 9-12 h to synthesize a leveling agent.
A leveling agent was synthesized in the same manner as in Example 4, except that 1,4-butanediol and urea were used instead of 1,3-dichloro-2-propanol and 2,6-diaminopyridine, respectively.
A leveling agent was synthesized in the same manner as in Example 4, except that poly(propylene glycol)diglycidyl ether (molecular weight: 380 g/mol) and thiourea were used instead of 1,3-dichloro-2-propanol and 2,6-diaminopyridine, respectively.
A leveling agent was synthesized in the same manner as in Example 4, except that 1,4-butanediol and aniline were used instead of 1,3-dichloro-2-propanol and 2,6-diaminopyridine, respectively.
1,3-Dichloro-2-propanol (A) was added to and completely dissolved in methanol at a temperature of about 50-70° C. Next, aniline (B) was added in a weight ratio of 4:1 (A:B) relative to the 1,3-dichloro-2-propanol. The reaction was allowed to proceed for about 9-12 h to synthesize a leveling agent.
A leveling agent was synthesized in the same manner as in Example 8, except that 1,4-butanediol and 1,3-diphenylurea were used instead of 1,3-dichloro-2-propanol and aniline, respectively.
A leveling agent was synthesized in the same manner as in Example 8, except that 1,6-hexanediol and 1,3-diphenylurea were used instead of 1,3-dichloro-2-propanol and aniline, respectively.
An electroplating composition including the following components was prepared: 100-150 g/L of copper sulfate pentahydrate, 100-150 g/L of sulfuric acid, 40-50 mg/L of hydrochloric acid, 1-3.5 ml/L of bis(sodium sulfopropyl)disulfide, 10 ml/L of a carrier, and 10 ml/L of the leveling agent synthesized in Example 1.
An electroplating composition was prepared in the same manner as in Preparative Example 1, except that the leveling agent of Example 2 was used instead of the leveling agent of Example 1.
An electroplating composition was prepared in the same manner as in Preparative Example 1, except that 1,1′-dibenzyl-4,4′-bipyridinium dichloride hydrate was used instead of the leveling agent of Example 1.
An electroplating composition was prepared in the same manner as in Preparative Example 1, except that Evans blue as a dye leveling agent was used instead of the leveling agent of Example 1.
An electroplating composition was prepared in the same manner as in Preparative Example 1, except that 2-mercaptopyridine was used instead of the leveling agent of Example 1.
An electroplating composition was prepared in the same manner as in Preparative Example 1, except that KDY2 (Dicolloy®) was used instead of the leveling agent of Example 1.
An electroless copper seed layer was formed on a substrate, followed by a series of curing/exposure/development/etching processes to form a photoresist circuit pattern. Then, the photoresist circuit pattern was plated with each of the electroplating compositions prepared in Preparative Examples 1-2 and Comparative Preparative Examples 1-4. Thereafter, the photoresist was removed to form a copper circuit pattern. The electroplating conditions were set as follows:
The cross-section of the copper circuit pattern was observed with an optical microscope. The results are shown in
The thickness deviations of the copper circuit patterns formed in Experimental Example 1, the flatnesses of the circuit patterns at the lines with narrow widths, and the flatnesses of the circuit patterns at the lines with wide widths were calculated according to the following equations:
Thickness deviation (μm)=A−B (1)
Flatness of circuit pattern at line with narrow width (%)=(A−B)/A×100 (2)
Flatness of circuit pattern at line with wide width (%)=(C−D)/C×100 (3)
The results are shown in Table 1.
As can be seen from the results in Table 1, the thickness deviations of the circuit patterns formed with the electroplating compositions of Preparative Examples 1 and 2, each including the inventive leveling agent, were smaller and the flatnesses of the circuit patterns were much lower. These results support that the use of the inventive leveling agents enables the formation of uniform circuit patterns with constant thicknesses.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0088379 | Jul 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/009067 | 6/24/2022 | WO |
